DE3613304C2 - Anionic disazo compounds - Google Patents

Description

The present invention relates to sulfo-containing diazo compounds and their salts, Manufacturing processes, their use as direct dyes and dyeing preparations thereof.

The invention therefore relates to compounds of the formula (I)

or a salt thereof, wherein
D the remainder of a diazo component from the benzene or naphthalene series,
X is a bridge member in the meaning -CO-, -CH₂-, -SO₂-, CONR₁- or

wherein Y is halogen, hydroxy, amino, C _1-4 alkoxy, phenoxy, an aliphatic, cycloaliphatic, aromatic or heterocyclic amine radical, the latter being C- or N-bonded, containing one to three heteroatoms and one to three C _1-4 alkyl groups can be substituted, and
K is the remainder of a heterocyclic coupling component or a CH-acidic enolizable compound,
n for 1, 2, 3 or 4,
a and b independently of one another, for 0 or 1,
R₁ is hydrogen, C _1-4 alkyl or substituted C _1-4 alkyl,
R₂ and R₃ independently, for hydrogen, halogen, C _1-4 alkyl, substituted C _1-4 alkyl, C _1-4 alkoxy, substituted C _1-4 alkoxy, -NHCORH, NH₂, a substituted amino group or quaternary ammonium group,
R₄ is hydrogen, C _1-4 alkyl, C _1-4 alkoxy, halogen or nitro, and
R₅ is C _1-4 alkyl, substituted C _1-4 alkyl, C _1-4 alkoxy or NH₂, or a mixture of compounds of formula (I) which are present as free acid or in salt form.

In a compound of formula (I), n is preferably at least two. D preferably contains as the remainder of a diazo component at least one sulfo group, but additionally Rings A and B (provided a and b are 0) and K bear a sulfo group.

Also included is the possibility that in a compound of formula (I) in addition to n Sulfo groups basic or cationic groups are present. In this case the Condition that the number of sulfo groups present in the molecule is equal to or greater than the number of basic and / or cationic groups present must be.

In the present description, halogen means fluorine, chlorine or bromine, in particular chlorine.

Unless otherwise stated, each alkyl or alkylene can be linear or branched.

D preferably denotes Da as a group of the formula (a), (b) or (c)

wherein
R₆ is hydrogen or sulfo, and
R₇ is hydrogen, halogen, C _1-4 alkyl, C _1-4 alkoxy or -NHCOC _1-4 alkyl, and
x for 0 or 1 and
y represents 1 or 2;
more preferably D is Db as a group of the formula (a₁), (b₁) or (c₁)

wherein R₇a represents hydrogen, chlorine, methyl, methoxy or -NHCOCH₃;
(b₁) as a group of formula (b) wherein, when (x + y) is 2, the sulfo groups are in positions 1,5; 3.6; 4.8; 5,7 and 6,8, and when (x + y) stands for 3, the sulfo groups are in positions 3, 6, 8 or 4, 6, 8;
(c₁) as a group of formula (c) wherein, when y is 1, the sulfo groups are in positions 3,6; 4.6; 3.8 or 4.8, and when y is 2, the sulfo groups are in positions 3, 6, 8;
more preferably D is Dc as a group of the formula (a₂) or (b₂)

(b₂) as a group of formula (b), wherein when (x + y) is 2, the sulfo groups are in the Positions 4, 8 or 6, 8 are located.  

D is particularly preferably Dd as a group of the formula (b₂), the group 6,8-disulfonaphthyl- (2) is very particularly preferred.

Y preferably represents Ya in the meaning chlorine, hydroxy, methoxy, amino, mono-C _1-2 -alkylamino, monohydroxy-C _2-4 -alkylamino, di (hydroxy-C _2-4 -alkyl) amino, anilino, morpholino , Piperidino, piperazino or N-methylpiperazino.

X is preferably the bridge Xb in the meaning -CO-, -SO₂ or

X particularly preferably represents -CO-.  

K as the residue of a heterocyclic compound preferably means the Rest of a coupling component from the pyrazole, pyridone or Barbi tursic acid series. K as the residue of a CH-acidic enolizable compound means preferably the rest of a coupling component from the aceto acetamide series.

K preferably represents Ka as a group of the formula (d), (e), (f) or (g),

wherein
Y₁ for OH or NH₂,
R₈ for C _1-4 alkyl, C _1-4 alkoxy, NH₂, CONH₂, COOR₁, phenyl or substituted phenyl,
R₉ is hydrogen, C _1-4 alkyl, phenyl or substituted phenyl;

Q₁ for hydrogen, CN, NH₂, -NHC _1-4 alkyl, OH, C _1-4 alkoxy, C _1-4 alkyl, C _2-4 alkyl monosubstituted by hydroxy or C _1-4 alkoxy, C _5-6 cycloalkyl; Phenyl or phenyl-C _1-4 alkyl, the phenyl ring of which is unsubstituted or substituted by one to three groups from the series C _1-4 alkyl, C _1-4 alkoxy, halogen, COOH and SO₃H; a saturated or unsaturated, 5- or 6-membered heterocyclic ring which contains one to three heteroatoms, is unsubstituted or substituted by one to three C _1-4 alkyl groups and which is bonded directly or via a bridge member C- or N-, im Case that a

is present, the link is made via a bridge link; -COR₁₀ or - (CH₂) _1-3 R₁₁,
R₁₀ for OH, NH₂ or C _1-4 alkoxy,

R₁₂ is OH, NH₂, C _1-4 alkyl, C _1-4 alkyl monosubstituted by OH, halogen, CN or C _1-4 alkoxy; Phenoxy, phenyl or phenyl-C _1-4 alkyl, where the phenyl ring of the last three groups is unsubstituted or substituted by one to three groups from the series C _1-4 alkyl, C _1-4 alkoxy, halogen, COOH and SO₃H, stand;
Q₂ is hydrogen, CN, halogen, SO₃H, NO, NO₂, -NR₁₃R₁₄, C _1-4 alkyl substituted by OH, halogen, CN, C _1-4 alkoxy, phenyl, SO₃H or -OSO₃H mono-substituted C _1-4 -Alkyl; -SO₂NH₂, -COR₁₅, -CH₂NHCOR₁₆E₁, a group of the formula

wherein the two CO and SO₂ groups are each bound to ortho-positioned C atoms of an aromatic ring;
for a group containing the grouping

in which the ammonium ion is part of a 5- or 6-membered ring which contains one to three heteroatoms and which is unsubstituted or substituted by one or two methyl groups or by one of the groups NH₂, -NHC _1-4 -alkyl or N (C _{1 -4} alkyl) ₂;
or for a group of the formula

stands in what
R₁₇ is hydrogen, C _1-4 alkyl or substituted by OH, halogen, CN, C _1-4 alkoxy or phenyl mono-substituted C _1-4 alkyl,

Z₂ represents the radical necessary for the formation of a 5- or 6-membered ring, to which a further 5- or 6-membered carbocyclic or heterocyclic ring containing one or two heteroatoms may be fused;
or
Q₁ and Q₂ both together form a C₃ or C₄ chain, which may be another 5- or 6-membered ring fused;
R₁₃ and R₁₄, independently of one another, hydrogen, C _1-4 alkyl substituted by OH, halogen, CN, C _1-4 alkoxy or phenyl monosubstitu iertes C _1-4 alkyl; or -COR₁₆E₁,
R₁₅ for OH, NH₂, -NHC _1-4 alkyl, -N (C _1-4 alkyl) ₂, C _1-4 alkyl, C _1-4 alkoxy, phenyl or phenoxy, the phenyl ring of the last two Groups are unsubstituted or substituted by one to three groups from the series C _1-4 alkyl, C _1-4 alkoxy, halogen, COOH and SO₃H,
R₁₆ for C _1-6 alkylene,
E₁ represents hydrogen, halogen, a protonatable amino group, a quaternary ammonium group or a hydrazinium group, SO₃H or -OSO₃H;
Q₃ for hydrogen, CN, NO₂, -NR₁₈R₁₉, a saturated or unsaturated, 5- or 6-membered heterocyclic ring which contains one or two heteroatoms, is C- or N-bonded and which is unsubstituted or substituted by up to three methyl groups pen or by one of the groups NH₂, -NHC _1-4 -alkyl or -N (C _1-4 -alkyl) ₂; C _1-6 alkyl, C _2-4 alkenyl, C _2-4 alkynyl; C _1-6 alkyl monosubstituted by OH, CN, C _1-4 alkoxy, acetylamino, -COR₂₀, SO₃H or -OSO₃H; C _5-6 cycloalkyl; Phenyl or phenyl-C _1-4 alkyl, the phenyl ring of the last two groups being unsubstituted or substituted by one to three groups from the series C _1-4 alkyl, C _1-4 alkoxy, halogen, NO₂, NH₂, COOH and SO₃H; -C _1-6 alkylene-E₂,

R₁₈ and R₁₉, independently of one another, for hydrogen, C _1-4 alkyl, C _1-4 alkyl monosubstituted by OH, halogen, CN or C _1-4 alkoxy, or by one or two groups from the series halogen, C _1-4 alkyl and C _1-4 alkoxy substituted phenyl,
R₂₀ for OH or C _1-4 alkoxy,
E₂ for a protonatable amino group, a quaternary ammonium group, a hydrazinium group or a group

R₂₁ for E₃, -NHCOR₁₆E₃, -SO₂NHR₁₆E₃ or -CONHR₁₆E₃, each R₂₂, independently of one another, for halogen, NH₂ or an aliphatic amino group, and
E₃ represents a protonatable amino group, a quaternary ammonium group or a hydrazinium group;
Q₄ represents hydrogen or OH with the proviso that Q₁ and Q₄ do not simultaneously mean OH; and
P₁ represents unsubstituted or substituted phenyl or unsubstituted or substituted naphthyl.

R₁ preferably represents R _1a as hydrogen, methyl, ethyl or C _1-3 alkyl monosubstituted by hydroxy, chlorine, cyano, carboxy or sulfo; more preferred for R _1b as hydrogen, methyl or ethyl; in particular preferably R 1 is hydrogen.

Y₁ preferably means OH.

R₈ preferably denotes R _8a as methyl, methoxy, CONH₂, COOH, COOC _1-2 alkyl or phenyl; more preferably R _8b as methyl, COOH or CONH₂; R bevorzugt particularly preferably denotes methyl.

R₉ is preferably R _9a as hydrogen, methyl, phenyl or substituted phenyl, the 1 or 2 substituents from the series C _1-4 alkyl, C _1-4 alkoxy, chlorine, acetylamino, -NHCOR₁₆E₃, -SO₂NHR₁₆E₃, carboxy and Sulfo bears; more preferably R _9b as phenyl or substituted phenyl which carries 1 or 2 substituents from the series methyl, methoxy, chlorine and sulfo.

The group (d) preferably represents (d₁) of the formula

especially for (d₂) of the formula

The group (e) preferably represents (e₁) of the formula

where Y _{2a is} O, S, = NH or = N-CN.

Q₁ as alkyl or alkoxy preferably contains 1 or 2 carbon atoms and particularly preferably means methyl or methoxy. As substituted alkyl it is preferably a C _2-3 alkyl group which is monosubstituted by hydroxy or C _1-2 alkoxy. As cycloalkyl it preferably means cyclohexyl.

In a substituted phenyl or phenylalkyl group as Q₁ the phenyl ring preferably has one or two substituents from the series Methyl, methoxy, chlorine, COOH and SO₃H.  

As a heterocyclic ring, Q 1 is preferably a saturated one Morpholine, pyrrolidine, piperidine, piperazine or N-methylpipera tin ring which is C- or N-bonded; or, if unsaturated, be preferably a pyridine, triazine, pyridazine, pyrimidine or pyrazine ring, which is bound via a C or N atom, in the latter Case (if the bond is via an N atom) a methylene bridge is present.

R₁₀ preferably represents R _10a as OH, NH₂, methoxy or ethoxy. It is more preferably R _10b as OH or NH₂.

R₁₂ is preferably R _12a as OH, NH₂, methyl, ethyl, methoxy or ethoxy; more preferably R _12b as OH or NH₂.

R₁₁ preferably represents R _11a as CN, chlorine, SO₃H, -OSO₃H,

or -COR _12a ; more preferred for R _11b as SO₃H, -OSO₃H,

or -COR _12b .

Q₁ preferably represents Q₁ as hydrogen, CN, NH₂, OH, methyl, ethyl, 2-hydroxyethyl, 2-C _1-2 alkoxyethyl, methoxy, ethoxy, cyclohexyl; Phenyl or phenyl-C _1-2 alkyl, the phenyl rings of which can be substituted by one or two groups from the series methyl, methoxy, chlorine, COOH and SO₃H;

-COR _10a or - (CH₂) _1-2 R _11a . More preferably Q₁ is Q _1b as NH₂, methyl, ethyl, 2-hydroxyethyl, cyclohexyl, phenyl, phenyl-C _1-2 alkyl, -COR _10b or -CH₂R _11b .

Even more preferably Q₁ is Q _1c as NH₂, methyl, phenyl, phenyl ethyl or -CH₂SO₃H.

Most preferably Q₁ is methyl.

E₁, E₂ or E₃ as a protonatable amino group or quaternary ammonium group is preferably the group B₁. B₁ is a primary Amino group, a secondary or tertiary aliphatic, cycloaliphati  natural, aromatic or saturated, unsaturated or partially unsung saturated heterocyclic amino group, the heterocyclic amino group can be bonded via C or N; or match one de quaternary ammonium group.

B₁ as an aliphatic amino group is preferably a mono-C _1-4 alkyl or di (C _1-4 alkyl) amino group. The alkyl group is unsubstituted or monosubstituted by halogen, hydroxy, cyano, C _1-4 alkoxy or phenyl. As a cycloaliphatic amino group, it is preferably C _5-6 cycloalkylamino, the cycloalkyl group of which is unsubstituted or substituted by one or two C _1-2 alkyl groups.

An aromatic amino group is preferably phenylamino, the phenyl ring of which is unsubstituted or substituted by one or two groups from the group consisting of halogen, C _1-4 alkyl, C _1-4 alkoxy, SO₃H and COOH.

B₁ as a heterocyclic amino group which is bonded via an N or C atom preferably means a saturated, unsaturated or partially unsaturated 5- or 6-membered ring which contains one or two heteroatoms and which can be substituted by one or two C _{1 -4} alkyl groups.

B₁ is more preferably a group B₂, where B₂ is a protonatable amino group -NR₂₃R₂₄ or a quaternary ammonium group -N⊕R₂₅R₂₆R₂₇, wherein
R₂₃ and R₂₄, independently of one another, represent hydrogen, C _1-2 alkyl, unbranched hydroxy-C _2-3 alkyl or benzyl or
R₂₃ and R₂₄ together with the N atom to which they are attached form a pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazin ring,
R₂₅ and R₂₆, independently of one another, have one of the non-cyclic or cyclic meanings of R₂₃ and R₂₄ except hydrogen, and
R₂₇ represents methyl, ethyl or benzyl, or
R₂₅, R₂₆ and R₂₇ together with the N atom to which they are attached form a pyridinium ring which is unsubstituted or substituted by one or two methyl groups.

B₁ particularly preferably represents the group B₃, where B₃ stands for -NR _23a R _24a or -N⊕R _25a R _26a R _27a , in which
R _23a and R _24a , independently of one another, are hydrogen, methyl or ethyl, or R _23a and R _24a together with the N atom to which they are bound are a piperidine, morpholine, piperazine or N-methyl piperazine - form ring,
R _25a and R _26a , independently of one another, are methyl or ethyl, or R _25a and R _26a together with the N atom to which they are attached have one of the cyclic meanings of R _23a and R _24a ,
R _{27a represents} methyl or ethyl, or
R _25a , R _26a and R _27a together with the N atom to which they are attached form a pyridinium group which is unsubstituted or substituted by one or two methyl groups.

E₁ is preferably E _1a as hydrogen, chlorine, the group B₂ or SO₃H. It is more preferably E _1b as hydrogen, chlorine, the group B₃ or SO₃H.

R₁₃ and R₁₄ mean preferably, R _13a and R _14a, wherein R _13a and R _14a, C un interdependent, hydrogen, _1-2 alkyl substituted by OH, C _1-2 alkoxy or phenyl mono-substituted C _1-2 alkyl or -COR _16a E _1a , wherein R _{16a is} C _1-2 alkylene. They are more preferably R _13b and R₁₄b, where R _13b and R _14b , independently of one another, are hydrogen, methyl or -COR _16a E _1b .

R₁₅ is preferably R _15a as OH, NH₂, -NHCH₃, -N (CH₃) ₂, methyl, ethyl, methoxy or ethoxy. It is more preferably R _15b as NH₂, methyl, ethyl, methoxy or ethoxy.

Q₂ preferably represents Q _2a as hydrogen, CN, chlorine, SO₃H, -NR _13b R _14b , methyl, ethyl, C _1-2 alkyl mono substituted by OH, phenyl, SO₃H or -OSO₃H; -COR _15a , -CH₂NHCOR _16a E _1b or a group with the grouping

to form a pyridine, pyrimidine or Benzimidazole ring, which is unsubstituted or by methyl, NH₂, -NHCH₃ or -N (CH₃) ₂ is monosubstituted.  

More preferably Q₂ is Q _2b as

It is even more preferably Q _2c as

Especially Q₂ is preferably hydrogen.

Q₁ and Q₂ also preferably form as Q _1a and Q _2a together with the C atoms to which they are attached, the part of a further ring according to the formula

d. H. for example a ring of the formula

with Y₃ as

R₁₈ and R₁₉ are preferably R _18a and R _19a , where R _18a and R _19a , independently of one another, stand for hydrogen, methyl, ethyl or phenyl.

R₂₀ is preferably R _20a as OH, methoxy or ethoxy.

An aliphatic amino group as R₂₂ is preferably a mono-C _1-4 alkyl or di (C _1-4 alkyl) amino group, in which the alkyl groups by halogen, OH, CN, C _1-4 alkoxy or Phenyl can be monosubstituted.

R₂₂ preferably represents R _22a , each R _22a , independently of one another, chlorine, NH₂, -NHC _1-2 -alkyl or -N (C _1-2 -alkyl) ₂, wherein the alkyl groups are unsubstituted or by OH, CN or C _1-2 alkoxy are monosubstituted. It is more preferably R _22b , each R _22b , independently of one another, being chlorine, NH₂, -NHCH₃, -N (CH₃) 2, -NHCH₂CH₂OH or -N (CH₂CH₂OH) ₂.

E₂ is preferably E _2a as group B₂ or as a group of the formula

more preferably for E _2b as group B₃ or as a group of the formula

E₃ is preferably E _3a as group B₂; more preferably E _3b as group B₃.

R₂₁ preferably represents R _21a as E _3a , -NHCOR _16a E _3a , -SO₂NHR _16a E _3a or -CONHR _16a E _3a ; more preferably for R _21b as E _3b , -NHCOCH₂E _3b or -CONHCH₂E _3b .

Q₃ preferably represents Q _3a as hydrogen, -NR _18a R _19a , phenyl, phenyl-C _1-2 alkyl, cyclohexyl; C _1-4 alkyl, mono-substituted C _1-4 alkyl by OH, CN, C _1-2 alkoxy, COR _20a , SO₃H or -OSO₃H; -C _1-3 -alkylene-E _2a ,

further preferred for Q₃b as hydrogen, -NHR _18a , phenyl-C _1-2 alkyl, methyl, ethyl, monosubstituted by OH, SO₃H or COR _20a

Most preferably Q₃ is hydrogen.

The group (f) preferably represents (f 1) of the formula

with the condition that Q₁ and Q₄ are not OH at the same time; more preferably for (f₂) of the formula

even more preferred for (f₃) of the formula

group (f) particularly preferably represents (f₄) of the formula

wherein Q _2c very particularly preferably represents hydrogen.

In the group of formula (g) P₁ is preferably P _1a as phenyl, phenyl substituted by one to three groups from the series chlorine, C _1-4 alkyl, C _1-4 alkoxy, carboxy and sulfo; 1- or 2-naphthyl which is unsubstituted or carries one or two substituents from the series consisting of chlorine, methoxy, carboxy, sulfo and phenylamino; more preferably it means P _1b as phenyl, phenyl monosubstituted by chlorine, methyl, methoxy or sulfo, 1- or 2-naphthyl which carries one or two sulfo groups; it particularly preferably means P _1c as phenyl, phenyl monosubstituted by methoxy or sulfo or monosulfo-1- or -2-naphthyl.

The group (g) preferably represents (g₁) of the formula

more preferably for (g₂) as group (g₁), wherein P _{1a is} P _1b ; in particular for (g₃) as a group (g₁), in which P _{1a stands} for P _1c .

More preferably, K is Kb as a group (d₁), (e₁), (f₁) or (g₁); more preferably for Kc as a group (d₂), (e₁), (f₂) or (g₂); even more preferred for Kd as group (e₁), (f₃) or (g₃); especially before for Ke as group (f (), wherein Q₂c particularly preferably hydrogen means.

In the ring A, R₂ and R₃ are preferably para to each other according to the formula

R₂ or R₃ as halogen is preferably chlorine; as alkyl or alkoxy it preferably means methyl or methoxy. As a substituted alkyl it is preferably C _1-4 alkyl monosubstituted by SO₃H, or the group - (CH₂) _1-3 -E _3b . As a substituted C _1-4 alkoxy, it is preferably monosubstituted by SO₃H. R₂ or R₃ as a substituted amino group or quaternary ammonium group preferably represents the group E _3b , more preferably a quaternary ammonium group.

R₅ as substituted alkyl is preferably the group - (CH₂) _1-3 -E _3b .

R₅ is preferably R _5a as methyl, methoxy, NH₂ or - (CH₂) _1-3 -E _3b . It is more preferably R _5b as methyl or NH₂.

R₂ is preferably R _2a as hydrogen, chlorine, methyl, methoxy, -NHCOR _5a , - (CH₂) _1-3 -SO₃H, -O (CH₂) ₃-SO₃H or - (CH₂) _1-3 -E _3b . Further, it is preferably R _2b as hydrogen, methyl, methoxy, -NHCOCH₃ or -NHCONH₂. R₂ particularly preferably represents R _2c as hydrogen or methyl.

R₃ is preferably R _3a as hydrogen, methyl or methoxy.

R₄ is preferably R _4a as hydrogen, methyl, methoxy or chlorine; in particular R₄ means hydrogen.

The azo group in ring B is expediently in 3 or 4 digits tion based on the C atom bonded to X, preferred is the para linkage.

Preferred compounds correspond to formula Ia,

wherein the azo group is bonded in the 3- or 4-position.

Further preferred compounds of the formula Ia are those in which

• (1) Db is Dc;
• (2) Db is Dd;
• (3) Kc is Kd;
• (4) those of (1) to (3), wherein the azo group is in the 4-position is bound;
• (5) those of (4), wherein R _{2b is} R _2c ;
• (6) those of (4), wherein R _{1b is} hydrogen;
• (7) those of (1) to (6), wherein Kc is Ke.

The compounds of formula I according to the invention can be used as free Acid, as an alkali metal salt or as any ammonium salt gene, in particular mixed salts are also possible, or it internal salt formation can also occur. Containing in salts as Cation substituted ammonium, this can be from a primary, derive secondary or tertiary amine, for example following amines are suitable: mono-, di- or tri-methyl-, -ethyl-, -pro pyl or butyl amine; Mono-, di- or tri-ethanol-, -propanol-  or isopropanol amine; N-methyl-N-hydroxyethylamine, N-methyl-N, N-di- (hydroxyethyl) amine, N-ethyl-N-hydroxyethoxyethylamine, morpholine, Piperidine, piperazine, hydroxyethylmorpholine, hydroxyethylpiperazine, Aminoethylpiperazine; Ethylenediamine, hexamethylenediamine; Dimethyl aminopropylamine, diethylaminopropylamine, diethylene glycolamine, Diglycolamine and 3-methoxypropylamine.

Polyglycolamines are also suitable as amines, for example by Reaction of ammonia, alkyl or hydroxyalkylamine with alkylene oxides can be obtained.

A quaternary ammonium ion can also be used as the substituted ammonium ion are present, which is derived from ammonium compounds, which is preferred contain one or two quaternary ammonium ions; for example to be mentioned: tetramethyl-, tetraethyl-, trimethylethyl-, dimethyl-di (2-hy droxypropyl) -, trimethylhydroxyethyl, tetrahydroxyethyl and tri methylbenzyl ammonium hydroxide.

The compounds of the formula I or mixtures thereof are prepared by removing the diazonium salt of one or more aminoazo compounds of formula II

with a compound of formula III

or a mixture of compounds of the formula III, where the symbols are as defined above and p for 1, 2, 3 or 4, q stand for 0, 1, 2 or 3 and the sum (p + q) stands for 1, 2, 3 or 4, implements.  

The starting compounds of formula II are either known or they are can be analogous to known methods from known starting materials are preserved.

The coupling components of formula III are known or can analogous to processes known per se from available starting materials getting produced. For example, coupling components from the Pyridone series according to formula IIIa

wherein Q₃x for -C _1-6 alkylene-E₂ or the group

stands, can be obtained by using a compound of formula IIIb,

where W is C _1-6 alkylene, a group

with R₂₈ as -NHCOR₁₆-, -SO₂NHR₁₆- or -CONHR₁₆-, and X₀ for one functional group, preferably for a group that can be split off as an anion pe standing reacted with the amino compound E₂-H.

Diazotization and coupling reactions are known per se Methods carried out.

The diazotization is advantageously carried out in mineral acid, preferably hydrochloric acid medium at 0-20 ° C. The coupling is convenient at pH 3-10, preferably carried out at pH 4-8.  

The resulting compound of formula I can be obtained in the form of the Solution used per se; the solution can also by Spray drying can be converted into the solid. Furthermore, too the usual insulation method for dyes, salting out from the Solution, filtering and drying suitable.

The type of cations present in a compound of formula I. can be influenced procedurally in different ways. A Possibility is that according to the above procedure put diazonium salt filtered off and washed with water. The solid diazonium compound is then an aqueous slurry or Added solution of the coupling component, which is a basic salt, Lithium, sodium, potassium, ammonium hydroxide, one or more orga contains African amines or a quaternary ammonium compound. A another method is that by diazotization and coupling Compound of the formula I obtained and isolated as the sodium salt Mineral acid, preferably hydrochloric acid, converted into the free acid filtered and washed with water; then neutra lized and thereby in the desired alkali metal or any saturated ammonium salt. By only partial transfer leaves in the free acid and / or by gradual neutralization preserve any kind of salt mixture. Even the method of Resalting, the conversion of one salt form into another is applicable bar.

If the diazotization takes place instead of alkali metal nitrite with alkyl nitrites, nitrous oxide or mixtures of nitrogen oxide and acid fabric, so it is possible to find metal-ion-free solutions of the end products to manufacture. If desired, lie can be added by adding a cation corresponding base or an amine corresponding salts can be obtained.

The compounds according to the invention in the form of their water-soluble sal ze are used for dyeing or printing hydroxy groups or nitrogenous organic substrates. They serve, for example way for dyeing or printing fibers, threads or herge made textiles made of polyamide or cellulose material, e.g. B.  Cotton, exist or contain them, according to known Methods; Cotton is preferably made using the pull-out method colored, for example from a long or short fleet and in the case of room to Cooking temperature.

The printing is done by impregnating with a printing paste, which is compiled according to a known method.

The new dyes can also be used for dyeing or printing Leather, preferably of chrome-tanned leather types, as well as glass or Glass products with different chemical compositions sen can be used according to methods known per se. Except this is what the dyes can do in the manufacture of inks known method can be used.

However, the compounds of the formula I are particularly suitable for dyeing ben or printing on paper such. B. for the production of in the Bulk of colored, sized or unsized paper. But you can can also be used for dyeing paper by immersion. The dyeing and printing of paper is carried out according to known methods. The dyeings and prints obtained in each case (especially those on Paper) show good fastness properties.

The compounds of formula I can also be in the form of coloring preparations be used. This form of application is particularly useful for dyeing preferred by paper. Processing in stable liquid, preferred as aqueous, concentrated dye preparations can be in general known manner, advantageously by dissolving in suitable solutions means, optionally with the addition of an auxiliary agent, e.g. B. one hydrotropic compound or a stabilizer. Of special importance part is the possibility of producing such stable, aqueous-concentrated preparations in the course of dye synthesis themselves without intermediaries insulation of the dye by, for example, the coupling in In the presence of suitable amines and especially quaternary ammoni Umhydroxide, the introduction of appropriate cations as further serve above, and optionally further hydrotropic auxiliary medium done.  

Suitable hydrotropic auxiliaries are, for example, low molecular weight Amides, lactones, alcohols, glycols or polyols, low molecular weight Ethers or oxyalkylation products and nitriles or esters; in Be traditional costumes preferably include methanol, ethanol, propanol; Ethylene, Propylene, diethylene, thiodiethylene and dipropylene glycol; Butanediol; β-hydroxypropionitrile, pentamethylene glycol, ethylene glycol monoethyl and propyl ether, ethylenediglycol monoethyl ether, triethy lenglycol monobutyl ether, butyl polyglycol, formamide, dimethylformamide, Pyrrolidone, N-methylpyrrolidone, glycol acetate, butyrolactone, urea and ε-caprolactam.

Hydrotropic compounds are e.g. B. described by H. Rath and S. Müller, Melliand Textilberichte 40, 787 (1959) or from E.H. Daruwalla in K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. VIII, p. 86-92 (1974).

Due to the additional content of a hydrotropic compound the storage stability of the dye preparation or the solubility further improve the dye used.

A favorable composition of such liquid preparations is, for example, the following (parts mean parts by weight):
100 parts of a compound of formula 1 as a water-soluble salt,
1-100, preferably 1-10 parts of an inorganic salt,
100-800 parts of water,
0-500 parts of one of the hydrotropic compounds listed above.

The liquid preparations can vary depending on the salt form as a suspension or preferably as real solutions. The preparations are stable and can be stored for a long time will.

Likewise, the compounds of formula 1 in a manner known per se are processed into solid, preferably granulated, dye preparations, advantageous by granulating as in the French patent No. 1,581,900.  

A favorable composition for solid preparations is, for example, the following (parts mean parts by weight):
100 parts of a compound of formula 1 as a water-soluble salt,
1-100, preferably 1-10 parts of an inorganic salt,
0-800 parts of an adjusting agent (preferably non-ionic such as starch, dextrin, sugar, glucose or urea).

In the solid preparation, there can still be up to 10% residual moisture to be available.

Depending on the cation present, the dyes of the formula I have or Cation mixture good solubility properties and then stand out particularly good solubility in cold water. They continue coloring the waste water in the production of both glued and unsized Paper practically not at all or only slightly. They mist up Not paper, are largely insensitive to filler and pH fluctuations and are only slightly inclined to colored two-sided paper. The dyeings on paper show good lightfastness after long periods of use the nuance changes tone-on-tone. The colored papers are very good wet fastness not only against water but also against milk, Fruit juices, sweetened mineral water and tonic water, and own too good alcohol fastness. The dyes have high substantivity, d. H. they are practically quantitative and show good results Building capacity; you can directly the pulp, d. H. without priori dissolve as dry powder or granules without that a decrease in brilliance or a decrease in color booty entry. However, such real solutions of the Dyes as mentioned above are used, which are stable, from lower Viscosity and therefore very easy to dose.

Fibers that contain wood pulp are mixed with the dyes of present invention dyed in good and level quality.

The colored papers are both oxidatively and reductively pale cash, what for the reuse of scrap and waste paper from Importance is.  

The following examples serve to illustrate the invention. Like this unless otherwise stated, parts in the examples mean Parts by weight or volume and percentages by weight or volume; the temperatures are given in degrees Celsius.

example 1

40.7 parts of the aminoazo dye produced by weakly acidic Coupling of diazotized 2-aminonaphthalene-6,8-disulfonic acid Aniline-ω-methanesulfonic acid and subsequent saponification in alkali medium, are stirred in 500 parts of water and with some Drop of acetic acid adjusted to pH 6.5. It is heated to 50 ° and Then drop 20 parts of 4-nitrobenzoyl chloride, dissolved in 200 parts Acetone, too. By adding sodium carbonate at the same time the pH kept at 6-7. Allow to stir for three hours and set the pH to 9 by adding sodium hydroxide solution. The precipitated dye is filtered off.

The press cake obtained is stirred in 500 parts of water. In the The resulting light yellow suspension is carried 40 parts crystallized Sodium sulfide and allowed to stir for two hours, one browning Liche suspension arises. The reduction ends after this time. A solution is formed by heating to 90 °. This solution continues 50 parts of sodium chloride are added and the mixture is stirred cold. The fancy The dye is filtered off, washed with brine and dried. Man he holds the aminoazo compound according to the formula

10.5 parts of this compound are dissolved in 100 parts of water and mixed with 1.5 parts of sodium nitrite. This reaction mixture pours into a template made of 200 parts of ice and 10 parts of 30% hydrochloric acid re. This creates a viscous, dark diazo suspension, the three  Stirred at 0-5 ° for hours. To destroy excess 1 part of sulfamic acid is added to nitrite. Then you wear 3 parts of 4-methyl-6-hydroxypyridone- (2) and increased by dropping from 30% sodium hydroxide to pH 7-8, whereupon the coupling starts. The clutch is finished after two hours. The fancy dye is filtered, washed with brine and dried. You get that Dye according to the formula,

which is strong in color and colors paper pulp in neutral yellow tones. The Colorings are characterized by high wet fastness and very good light authenticity.

Example 2

The procedure is as in Example 1 and uses instead of 3 parts the pyridone compound 5.7 parts of 3-methyl-1-phenyl-5-pyrazolon-4'-sul fonic acid, this gives the dye of the formula

stains the paper mass in golden yellow tones. Draw the colors is characterized by high wet and light fastness.  

Examples 3 to 123 / Table 1

Analogous to the method shown in Examples 1 and 2, further ver Compounds of formula I using appropriate starting compound be manufactured.

They correspond to the formula (A)

for which the symbols are defined in Table 1 below. These dyes dye paper in greenish yellow to reddish yellow Tones; the dyeings show good light and wet fastness properties.

In particular, the dyes from Table 1 on paper receive the following colors:

• a) reddish yellow: for examples 6, 8, 10, 19, 25, 32, 41-46, 59-59, 62-65, 72, 74, 99, 104 and 106;
• b) golden yellow: for examples 5, 16, 18, 29, 33, 34, 40, 48, 68, 70, 79, 83, 90, 95, 103, 107, 119 and 123;
• c) neutral yellow: for examples 3, 4, 7, 9, 11-15, 17, 20-24, 26-28, 30, 31, 35-39, 47, 60, 61, 66, 67, 69, 71, 73, 75-78, 80-82, 84-89, 91-94, 96-98, 100, 101, 105, 108, 109, 113, 114 and 120-122;
• d) greenish yellow: for Examples 102, 110-112 and 115-118.

In the following tables 1 to 3, A⊖ represents an anion of the use deten reaction medium.  

Table 1

Compounds of formula (A)

Example 124

20 parts of 3-nitrobenzoyl chloride are mixed with 42 parts of the aminoazo color fabricated by coupling diazotized 2-aminonaph thalin-4,8-disulfonic acid on m-toluidine, condensed and then reduced with sodium sulfide. After done in the usual way Diazotization is coupled with 2.5 parts of 4-methyl-6-hydroxypyridone- (2) pelt. The dye is obtained according to the formula

colors the paper pulp in brilliant neutral yellow tones. The paper stains show good light and wet fastness properties.

Examples 125 to 143 / Table 2

Analogous to the method described in Example 124, further ver Compounds of formula i are prepared in the following Table 2 are listed. They correspond to formula (B)

where the symbols are defined in Table 2. Color these dyes Paper in greenish yellow to neutral yellow tones, the preserved Paper dyeings show good general fastness properties.  

Table 2

Compounds of formula (B)

Example 144

42 parts of the aminoazo dye produced by coupling dia quoted 2-aminonaphthalene-4,8-disulfonic acid with m-toluidine condensed with 25 parts of acetylaminobenzene-4-sulfochloride and on finally saponified alkaline. The product obtained is as usual diazotized and coupled to 2.5 parts of 4-methyl-6-hydroxypyridone- (2). It becomes the dye of the formula

preserved, which dyes paper in neutral yellow tones. Light and wet fastness of the dyeings is good.

Example 145

If one sets 40.7 parts of the aminoazo analogously to the method in Example 144 dye produced by coupling diazotized 2-amino naphthalene-4,8-disulfonic acid on aniline-ω-methanesulfonic acid closing alkaline saponification, so you get the dye the formula,

the neutral yellow paper dyeing of good light and wet fastness properties delivers.  

Example 146

40.7 parts of 2- (4'-aminobenzolazo) -naphthalene-4,8-disulfonic acid suspended in 400 parts of ice water and with 18.5 parts of cyanuric chloride transferred. The mixture is stirred for three hours at 0-5 °, the pH kept at 5-6 with sodium hydroxide solution. After two hours the condensate is tion ended. 14 parts of 3-nitroaniline are then added and the mixture is warmed up slowly to 80 ° and keeps the pH at 6-7. After another six hours practically no starting material is detectable. To get the th suspension is then slowly added 40 parts of sodium sulfide, whereupon reduction of the nitro group begins. Upon completion of the Reduk tion is allowed to cool with stirring and the precipitate is sucked best starting from the compound of the formula

from. The product thus obtained is then in 200 parts of water touched. This mixture is concentrated with 20 parts. Hydrochloric acid acidifies and then dropwise with 25 parts of 4N sodium nitrite solution transferred. This diazo suspension is allowed to stir for three hours. Like this then one enters 13 parts of 4-methyl-6-hydroxypyridon- (2) and provides adjust the pH to 8-9 with sodium hydroxide solution. There is coupling to a yellow Dye that is filtered off, washed with brine and dried. The dye obtained corresponds to the formula

it dyes paper pulp in neutral yellow tones. These paper stains are characterized by high light and wet fastness.  

Examples 147 to 155 / Table 3

Analogously to the method described in example 146, further methods can be used Compounds of formula I are prepared as follows Table 3 are listed. This can be done on the triazine ring dene chlorine atom if desired by methods known per se can be replaced, for example by implementation with any gene amine and preferably with mono- or diethanolamine. The Ver bonds correspond to formula (C),

wherein the symbols are defined in Table 3 below. This Dyes dye paper pulp in neutral yellow tones that get Paper stains show good light and wet fastness properties create.

Table 3

Compounds of formula (C)

The dyes of Examples 1-155 fall due to the selected Her conditions as sodium salts (provided that none internal salt formation can occur) and are isolated as such. she can however also in other salt form or mixed salt form can be obtained by converting to the free acid with the compound (s) containing the desired cation (s) converts or the sodium salt of a corresponding salting subjects, thereby causing one or more of those described in the description to continue be introduced as preferred cations.

Example 156

The dye prepared according to Example 1 is in before drying 200 parts of water are mixed and mixed with 20 parts of 30% hydrochloric acid puts. After stirring for a long time, the dye is in the form of the free Filtered off acid and into a mixture of 8 parts of diglycolamine and 5 Share ethylene glycol entered. The dye goes under heat-free put in solution. It is adjusted to 90 parts with water and obtained such a ready-to-use, storage-stable dye solution.

Example 157

Is used instead of the amine / glycol Ge used in Example 156 mixed lithium hydroxide solution, so you get a liquid-aqueous Dyeing preparation containing the dye according to Example 1 as a lithium salt contains.

Analogous to the method described in Examples 156 and 157 also the dyes of Examples 2-155 in liquid-aqueous dyeing ready to be transferred with high shelf life.

Possible applications of the compounds according to the invention and liquid-aqueous dye preparations thereof are described in the following writings illustrated.  

Staining instructions A

in a Dutch company 70 parts of chemically bleached sulfite cellulose made of softwood and 30 parts of chemically bleached sulfite cellulose Birchwood ground in 2000 parts of water. Scatter to this mass 0.2 part of the dye from Example 1 or 2 or gives 1.0 part of the liquid dye preparation according to Example 156 or 157. After 20 minutes of mixing, paper is made from it. That on this Absorbent paper obtained in this way is neutral yellow (or golden yellow) colors. The wastewater is practically colorless.

Dyeing Instructions B

0.5 part of the dye powder from Example 1 or 2 is in 100 Dissolve hot water and cool to room temperature. The Solution is added to 100 parts of chemically bleached sulfite cellulose, which was ground in a Dutchman with 2000 parts of water. After 15 Minutes are mixed in the usual way with resin glue and aluminum glued sulfate. Paper made from this material shows a neutral yellow (or golden yellow) color and has good Sewage and wet fastness properties.

Coloring instructions C

An absorbent paper web made from unsized paper is drawn at 40-50 ° through a dye solution of the following composition:
0.5 part of the dye from Example 1 or 2 or of the liquid preparation from Example 156 or 157,
0.5 parts starch and
99.0 parts water.

The excess dye solution is squeezed out by two rollers. The dried paper web is colored neutral yellow (or golden yellow).

In an analogous manner as specified in regulations A to C can also with the dyes of the other examples or with a dye preparation tion of it. The paper colorations obtained are yellow colored and have a high level of authenticity.  

Dyeing instructions D (leather)

100 parts of intermediate dried chrome suede are in a flot te from 400 parts of water, 2 parts of 25% ammonium hydroxide solution and 0.2 parts of a commercial wetting agent for one hour Tumbled 50 ° in the barrel. The fleet is then drained. The ge 400 parts of water from 60 ° and 1 part of 25% ammonium hydroxide solution added. After the Zu Set of 5 parts of the dye from Example 2, dissolved in 200 parts Water, stained at 60 ° for 90 minutes. Then be slow 50 parts of 8% formic acid were added to acidify the pH. The Treatment then continues for another 30 minutes. From finally the leather is rinsed, dried and in the usual way mangled. The yellow leather dye obtained is dyed and does not matter shows good light fastness.

Dyeing Instructions E (Cotton)

To a dyeing liquor consisting of 3000 parts of softened water, 2 Parts of soda and 1 part of the dye from Example 2 are at 30 ° Given 100 parts of pre-wetted cotton fabric. After adding 10 Tei len Glauber's salt will bring the fleet to boiling point within 30 minutes heated temperature, during this heating process to the tempe maturation levels 50 ° and 70 ° each added a further 10 parts Glauber's salt will. The dyeing is then continued at boiling temperature for a further 15 minutes continued, finally 10 parts Glauber's salt are added. The dye bath is then allowed to cool. At 50 ° the dyed fabric removed from the liquor, rinsed with water and dried at 60 °. A golden yellow cotton dyeing of good light and wet is obtained authenticity.  

Dyeing instructions F (polyamide)

0.1 part of the dye from Example 2 in 300 parts of water solved. 0.2 parts of ammonium sulfate are added to this solution and the mixture is left with the pre-wetted textile fabric (5 parts wool gabardine or 5 parts Nylon satin) in this bath, which will take you over 30 minutes which is heated. The bath is boiled for 30 minutes kept, the water evaporated during the dyeing process is continuous only replaced. Finally, the dyed fabric from the Removed liquor and rinsed with water. Received after drying you get a golden yellow polyamide dye that has good light and wet fastness properties shows.

In an analogous manner as described in regulations D to F, can also be dyed with the dyes of the other examples. Which he substrates dyed in yellow tones show good fastness egg properties.

Claims (14)

1. Compounds of formula (I) or a salt thereof, wherein
D the remainder of a diazo component from the benzene or naphthalene series,
X is a bridge member in the meaning -CO-, -CH₂-, -SO₂-, CONR₁- or wherein Y is halogen, hydroxy, amino, C _1-4 alkoxy, phenoxy, an aliphatic, cycloaliphatic, aromatic or heterocyclic amine radical, the latter being C- or N-bonded, containing one to three heteroatoms and one to three C _1-4 alkyl groups can be substituted, and
K is the remainder of a heterocyclic coupling component or a CH-acidic enolizable compound,
n for 1, 2, 3 or 4,
a and b independently of one another, for 0 or 1,
R₁ is hydrogen, C _1-4 alkyl or substituted C _1-4 alkyl,
R₂ and R₃ independently, for hydrogen, halogen, C _1-4 alkyl, substituted C _1-4 alkyl, C _1-4 alkoxy, substituted C _1-4 alkoxy, -NHCORH, NH₂, a substituted amino group or quaternary ammonium group,
R₄ is hydrogen, C _1-4 alkyl, C _1-4 alkoxy, halogen or nitro, and
R₅ is C _1-4 alkyl, substituted C _1-4 alkyl, C _1-4 alkoxy or NH₂, or a mixture of compounds of formula (I) which are present as free acid or in salt form. 2. Compounds according to claim 1, wherein D represents Da as a group of the formula (a), (b) or (c) wherein
R₆ is hydrogen or sulfo, and
R₇ is hydrogen, halogen, C _1-4 alkyl, C _1-4 alkoxy or -NHCOC _1-4 alkyl, and
x for 0 or 1, and
y stands for 1 or 2. 3. Compounds according to claim 1 or 2, wherein
X stands for Xb as a bridge -CO-, -SO₂- or with Ya in the meaning of chlorine, hydroxy, methoxy, amino, mono-C _1-2 -alkylamino, monohydroxy-C _2-4 -alkylamino, di (hydroxy-C _2-4 -alkyl) amino, anilino, morpholino, Piperidino, piperazino or N-methylpiperazino. 4. Compounds according to any one of claims 1 to 3, wherein K is Ka as a group of the formula (d), (e), (f) or (g), wherein
Y₁ for OH or NH₂,
R₈ for C _1-4 alkyl, C _1-4 alkoxy, NH₂, CONH₂, COOR₁, phenyl or substituted phenyl,
R₉ represents hydrogen, C _1-4 alkyl, phenyl or substituted phenyl,
Y₂ for O, S, = NH, = N-CN or Q₁ for hydrogen, CN, NH₂, NHC _1-4 alkyl, OH, C _1-4 alkoxy, C _1-4 alkyl, C _2-4 alkyl substituted by hydroxy or C _1-4 mono, C _{5- 6-} cycloalkyl; Phenyl or phenyl-C _1-4 alkyl, the phenyl ring of which is unsubstituted or substituted by one to three groups from the series C _1-4 alkyl, C _1-4 alkoxy, halogen, COOH and SO₃H; a saturated or unsaturated, 5- or 6-membered heterocyclic ring containing one to 3 hetero atoms, is unsubstituted or substituted by one to three C _{1- 4} alkyl groups and which is bonded N-directly or via a bridge member or C-, whereby in Case that a is present, the link is made via a bridge link; -COR₁₀ or - (CH₂) _1-3 R₁₁,
R₁₀ for OH, NH₂ or C _1-4 alkoxy,
R₁₁ for CN, halogen, SO₃H, -OSO₃H, -COR₁₂ or R₁₂ is OH, NH₂, C _1-4 alkyl, C _1-4 alkyl monosubstituted by OH, halogen, CN or C _1-4 alkoxy; Phenoxy, phenyl or phenyl-C _1-4 alkyl, where the phenyl ring of the last three groups is unsubstituted or substituted by one to three groups from the series C _1-4 alkyl, C _1-4 alkoxy, halogen, COOH and SO₃H, stand;
Q₂ for hydrogen, CN, halogen, SO₃H, NO, NO₂, -NR₁₃R₁₄, C _1-4 -alkyl, through OH, halogen, CN, C _1-4 -alkoxy, phenyl, SO₃H or -OSO₃H monosubstituted C _1-4 - Alkyl; -SO₂NH₂, -COR₁₅, -CH₂NHCOR₁₆E₁, a group of the formula wherein the two CO and SO₂ groups are each bound to ortho-positioned C atoms of an aromatic ring; for a group containing the grouping in which the ammonium atom is part of a 5- or 6-membered ring which contains one to three heteroatoms and which is unsubstituted or substituted by one or two methyl groups or by one of the groups NH₂, NHC _1-4 -alkyl or -N (C _{1- 4} alkyl) ₂; or for a group of the formula stands in what
R₁₇ is hydrogen, C _1-4 alkyl or substituted by OH, halogen, CN, C _1-4 alkoxy or phenyl mono-substituted C _1-4 alkyl,
Z₁ S, mean and
Z₂ represents the radical necessary for the formation of a 5- or 6-membered ring, to which a further 5- or 6-membered carbocyclic or heterocyclic ring containing one or two heteroatoms may be fused;
or
Q₁ and Q₂ both together form a C₃ or C₄ chain, which may be another 5- or 6-membered ring fused;
R₁₃ and R₁₄ independently of one another, hydrogen, C _1-4 alkyl monosubstituted by OH, halogen, CN, C _1-4 alkoxy or phenyl C _1-4 alkyl; or -COR₁₆E₁
R₁₅ for OH, NH₂, -NHC _1-4 alkyl, -N (C _1-4 alkyl) ₂, C _1-4 alkyl, C _1-4 alkoxy, phenyl or phenoxy, the phenyl ring of the last two Groups are unsubstituted or substituted by one to three groups from the series C _1-4 alkyl, C _1-4 alkoxy, halogen, COOH and SO₃H,
R₁₆ for C _1-6 alkylene,
E₁ represents hydrogen, halogen, a protonatable amino group, a quaternary ammonium group or a hydrazinium group, SO₃H or -OSO₃H;
Q₃ for hydrogen, CN, NO₂, -NR₁₈R₁₉, a saturated or unsaturated, 5- or 6-membered heterocyclic ring which contains one or two heteroatoms, is C- or N-bonded and which is unsubstituted or substituted by up to three methyl groups or by one of the groups NH₂, -NHC _1-4 -alkyl or -N (C _1-4 -alkyl) ₂; C _1-6 alkyl, C _2-4 alkylene, C _2-4 alkynyl; C _1-6 alkyl monosubstituted by OH, CN, C _1-4 alkoxy, acetylamino, -COR₂₀, SO₃H or -OSO₃H; C _5-6 cycloalkyl; Phenyl or phenyl-C _1-4 alkyl, the phenyl ring of the last two groups being unsubstituted or substituted by one to three groups from the series C _1-4 alkyl, C _1-4 alkoxy, halogen, NO₂, NH₂, COOH and SO₃H; -C _1-6 alkylene-E₂, R₁₈ and R₁₉ independently of one another, for hydrogen, C _1-4 -alkyl, by OH, halogen, CN or C _1-4 -alkoxy, monosubstituted C _1-4 -alkyl, phenyl or by one or two groups from the series halogen, C _1-4 alkyl and C _1-4 alkoxy substituted phenyl
R₂₀ for OH or C _1-4 alkoxy,
E₂ for a protonatable amino group, a quaternary ammonium group, a hydrazinium group or a group R₂₁ for E₃, -NHCOR₁₆E₃, -SO₂NHR₁₆E₃ or -CONHR₁₆E₃,
each R₂₂ independently of one another, for halogen, NH₂ or an aliphatic amino group, and
E₃ represents a protonatable amino group, a quaternary ammonium group or a hydrazinium group;
Q₄ represents hydrogen or OH with the proviso that Q₁ and Q₄ do not simultaneously mean OH, and
P₁ represents unsubstituted or substituted phenyl or unsubstituted or substituted naphthyl. 5. Compounds according to any one of claims 1 to 4, wherein R₁ represents R _1a as hydrogen, methyl, ethyl or C _1-3 alkyl monosubstituted by hydroxy, chlorine, cyano, carboxy or sulfo. 6. Compounds according to claim 1, wherein ring A R₂ and R₃ are para to each other according to the formula 7. A compound according to claim 6, wherein R₂ is R₂b in the meaning hydrogen, methyl, methoxy, -NHCOCH₃ or -NHCONH₂, and R₃ is R _3a in the meaning hydrogen, methyl or methoxy. 8. Compounds according to claim 1, wherein in ring B the azo group is in meta- or para position related to the C atom linked to the X bridge.   9. A process for the preparation of compounds of the formula (I), defined in claim 1 or mixtures thereof, characterized in that the diazonium salt of one or more aminoazo compounds of the formula (II) with a compound of formula (III) or a mixture of compounds of the formula (III),
wherein the symbols are as defined in claim 1 and p is 1, 2, 3 or 4, q is 0, 1, 2 or 3 and the sum (p + q) is 1, 2, 3 or 4. 10. The method according to claim 9, characterized in that the coupling reaction in the presence of a lithium salt, ammonium hydroxide, a primary, secondary or tertiary amine or a quaternary ammonium compound. 11. Use of a compound of formula (I), defined in claim 1, in water-soluble Form, for the production of a storage-stable, liquid-aqueous dye preparation.   12. Use of a compound of formula (I) defined in claim 1, or one Preparation according to claim 11 for dyeing or printing hydroxyl or nitrogenous organic substrates. 13. Use according to claim 12, characterized in that the substrate is paper, Glass or glass products, leather or textile material made of cellulose or polyamide exists or contains them, is used. 14. Use of a compound of formula (I), defined in claim 1, for the preparation of Inks.